US4150058A - Production of alkyl phosphines - Google Patents
Production of alkyl phosphines Download PDFInfo
- Publication number
- US4150058A US4150058A US05/904,027 US90402778A US4150058A US 4150058 A US4150058 A US 4150058A US 90402778 A US90402778 A US 90402778A US 4150058 A US4150058 A US 4150058A
- Authority
- US
- United States
- Prior art keywords
- catalyst
- alkyl
- alkyl amine
- phosphorus
- phosphines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 alkyl phosphines Chemical class 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000003003 phosphines Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical class PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000003956 methylamines Chemical group 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical class P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5004—Acyclic saturated phosphines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- This invention relates to a process for making alkyl phosphines of the general formula R n PH 3-n (I), in which R stands for different or identical alkyl groups having from 1 to 3 carbon atoms, preferably 1 carbon atom, and n stands for a whole number of 1 to 3.
- the reaction should preferably be effected at temperatures of 280° to 350° C.
- the proportions of starting reactants may be varied within wide limits. It is more particularly possible to use phosphorus, steam and alkyl amine in proportions corresponding to a molar ratio of P 4 :H 2 O:alkyl amine of 1:1:1 up to 1:30:30. It is also advantageous to pass the starting reactants through the reactor at a velocity necessary to ensure a contact time with the catalyst of 1 to 200 seconds, preferably 5 to 100 seconds.
- a further advantageous feature provides for the starting reactants to be mixed in gas phase, for the resulting mixture to be first heated to reaction temperature and to be then contacted with the catalyst.
- Active carbon especially active carbon having a BET-surface area of more than 10 m 2 /g, should preferably be employed as the catalyst.
- active carbon especially active carbon having a BET-surface area of more than 10 m 2 /g, should preferably be employed as the catalyst.
- the useful alkyl amines comprise more especially primary, secondary and tertiary methyl amines.
- the reaction should preferably be effected at atmospheric pressure or under the slight overpressure which is established upon the reactants being passed through the reactor.
- reaction products coming from the reactor can be worked up by conventional methods. More specifically, they can be separated from each other by distillation; or reaction gases containing products of different basicity can be scrubbed with an acid and these products separated via the resulting phosphonium salts. Unreacted starting materials can be recycled.
- alkyl ammonium phosphates which are formed by the reaction in accordance with equation (2) deposit on the catalyst, from which they can be removed by extraction with boiling water or dilute phosphoric acid. The catalyst can then be used again. The resulting phosphate solutions are admixed with sodium hydroxide solution so as to liberate the amines, which can be recycled.
- alkyl phosphines made in accordance with this invention are interesting starting materials for making flameretardant agents, pharmaceutical preparations and the like.
- Methyl phosphines of the formulae CH 3 PH 2 ; (CH 3 ) 2 PH and (CH 3 ) 3 P were made.
- reaction products coming from the reactor had different boiling points and a different basicity. They were separated from each other in known manner and the methyl phosphines were recovered in pure form. Unreacted starting material was recycled.
- the pure methyl phosphines had the following boiling points under 760 mm Hg:
- the phosphines were identified in the form of their phosphonium chlorides by NMR-spectroscopy (H- and P-resonances). The spectra were taken at 90 megahertz in a strong hydrochloric acid solution. The data indicated are rounded inasmuch as they slightly depend on the HCL-concentration.
- CH 3 PH 2 was made as the principal product under the conditions described in Example 1, save that the reaction temperature was 285° C. and the contact time was 35 seconds.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Alkyl phosphines are made. To this end, phosphorus in vapor form is reacted with steam and an alkyl amine at elevated temperature in contact with a carbon catalyst placed in a reactor, the reactants being used individually or in admixture with one another.
Description
This invention relates to a process for making alkyl phosphines of the general formula Rn PH3-n (I), in which R stands for different or identical alkyl groups having from 1 to 3 carbon atoms, preferably 1 carbon atom, and n stands for a whole number of 1 to 3.
Various processes for making alkyl phosphines have been described in the literature, which are all based on the alkylation of yellow phosphorus with an alkyl iodide or alkanol (Auger, V. C. R. Acad. Sci., Paris 139, 639, 671 (1904); Kosolapoff, G. M., Organophosphorus Compounds, Wiley (1950)). These processes are not, however, satisfactory inasmuch as the resulting phosphines are obtained in poor yields only and in addition to this are seriously contaminated by a series of phosphine derivatives.
In German Patent Specification "Offenlegungsschrift" No. 2,407,461, it has been suggested that PH3 should be converted with an alkyl halide by heterogeneous catalysis to an alkyl phosphine. Under the conditions used in this process, quaternary phosphonium halides are obtained as additional products which precipitate on the catalyst so that it is necessary for the latter to be frequently reactivated by extraction of the phosphonium salts.
It is also known that the reaction of elemental phosporus with an alkyl halide at 280° to 420° C. in contact with active carbon produces a mixture consisting substantially of mono- and dialkylhalogeno-phosphines, which is obtained together with monor proportions of trialkyl phosphonium halides which are capable of being reacted with an alkali metal hydroxide solution to give trialkyl phosphines (cf. German Pat. Specification No. 2,116,355 and German Pat. Specification "Offenlegungsschrift" No. 2,116,439).
A disadvantage which is encountered with the process just described resides in the fact that the trialkyl phosphines are obtainable in poor yields only.
It is therefore an object of this invention to provide a single step process permitting short chain alkyl phosphines, especially methyl phosphines, to be produced in high yields from readily accessible yellow phosphorus.
This object has unexpectedly been achieved by our present process which comprises: reacting phosphorus in vapor form with steam and an alkyl amine of the general formula Rn NH3-n (II), in which R and n have the meanings given above, at elevated temperature in contact with a carbon catalyst placed in a reactor, the reactants being used individually or in admixture with one another.
The reaction should preferably be effected at temperatures of 280° to 350° C. The proportions of starting reactants may be varied within wide limits. It is more particularly possible to use phosphorus, steam and alkyl amine in proportions corresponding to a molar ratio of P4 :H2 O:alkyl amine of 1:1:1 up to 1:30:30. It is also advantageous to pass the starting reactants through the reactor at a velocity necessary to ensure a contact time with the catalyst of 1 to 200 seconds, preferably 5 to 100 seconds. A further advantageous feature provides for the starting reactants to be mixed in gas phase, for the resulting mixture to be first heated to reaction temperature and to be then contacted with the catalyst. Active carbon, especially active carbon having a BET-surface area of more than 10 m2 /g, should preferably be employed as the catalyst. In order to produce predominantly primary phosphines, it is good practice to react the phosphorus with a slight stoichiometric excess of alkyl amine in contact with the catalyst over a short period of time, namely 5 to 50 seconds. Inversely, in order to produce predominantly tertiary phosphines, it is good practice to react the phosphorus with a large stoichiometric excess of the alkyl amine in contact with the catalyst over a long period of time, namely more than 50 up to about 100 seconds. The useful alkyl amines comprise more especially primary, secondary and tertiary methyl amines.
The reaction of phosphorus with water and simultaneously with an alkyl amine has not yet been described in the literature of which we are aware.
As already mentioned above, it is good practice to use 1 to 30 moles of H2 O and 1 to 30 moles of alkyl amine per mol of P4. In those cases in which the goal is to convert the phosphorus as completely as possible, e.g. in accordance with the following equations:
2P.sub.4 +12H.sub.2 O+5R.sub.3 N=5RPH.sub.2 +H.sub.3 PO.sub.4 +5R.sub.2 NH (1)
3h.sub.3 po.sub.4 +5r.sub.2 nh=alkyl ammonium phosphate (2)
it is naturally advantageous to use an excess of H2 and alkyl amine.
The reaction should preferably be effected at atmospheric pressure or under the slight overpressure which is established upon the reactants being passed through the reactor.
The reaction products coming from the reactor can be worked up by conventional methods. More specifically, they can be separated from each other by distillation; or reaction gases containing products of different basicity can be scrubbed with an acid and these products separated via the resulting phosphonium salts. Unreacted starting materials can be recycled.
The alkyl ammonium phosphates which are formed by the reaction in accordance with equation (2) deposit on the catalyst, from which they can be removed by extraction with boiling water or dilute phosphoric acid. The catalyst can then be used again. The resulting phosphate solutions are admixed with sodium hydroxide solution so as to liberate the amines, which can be recycled.
The process of this invention which is naturally not limited to the specific procedures described herein permits the production of commercial quantities of alkyl phosphines from readily accesible alkyl amines and more especially from commercially available yellow phosphorus.
The alkyl phosphines made in accordance with this invention are interesting starting materials for making flameretardant agents, pharmaceutical preparations and the like.
Methyl phosphines of the formulae CH3 PH2 ; (CH3)2 PH and (CH3)3 P were made. To this end, a mixture of 0.25 mol/h of P4, 3 mols/h of H2 O and 1 mol/h of (CH3)3 N was heated to 290° C. in a preheater and then contacted over a period of 83 seconds at 300° C. and at atmospheric pressure with an active carbon catalyst (particle size=0.5 to 2.0 mm), which was placed in a reactor.
The reaction products coming from the reactor had different boiling points and a different basicity. They were separated from each other in known manner and the methyl phosphines were recovered in pure form. Unreacted starting material was recycled.
A total quantity of 186 g of phosphorus was used. This gave
85 g of CH3 PH2,
64 g of (CH3)2 PH and
11 g of (CH3)3 P
corresponding to a P4 -yield of 80%, based on equation (1).
The pure methyl phosphines had the following boiling points under 760 mm Hg:
CH3 PH2 : -15° C.
(CH3)2 PH: 10°-21° C.
(CH3)3 P: 38°-40° C.
The phosphines were identified in the form of their phosphonium chlorides by NMR-spectroscopy (H- and P-resonances). The spectra were taken at 90 megahertz in a strong hydrochloric acid solution. The data indicated are rounded inasmuch as they slightly depend on the HCL-concentration.
__________________________________________________________________________
P-resonance
(based on H.sub.3 PO.sub.4 of 85%
H-resonance strength
__________________________________________________________________________
[CH.sub.3 PH.sub.3 ]Cl
δ CH.sub.3
2.1
δCH.sub.3 -P
71 Hz
δ PH
7.5
δP-H
555 Hz
δPH-CH.sub.3
5 Hz
δP+ 62
[(CH.sub.3).sub.2 PH.sub.2 ]Cl
δ CH.sub.3
2.0
δCH.sub.3 -P
16 Hz
δPH
6.5
δP-H
528 Hz δP+ 31
[(CH.sub.3).sub.3 PH]Cl
δCH.sub.3
1.95
δCH.sub.3 -P
15 Hz
δCH.sub.3 -PH
5.5Hz
δPH
6.4
δP-H
507 Hz δP-- 3
__________________________________________________________________________
CH3 PH2 was made as the principal product under the conditions described in Example 1, save that the reaction temperature was 285° C. and the contact time was 35 seconds.
A total quantity of 179 g of phosphorus was used. This gave
84 g of CH3 PH2
23 g of (CH3)2 PH
3.2 g of (CH3)3 P
corresponding to a P4 -yield of 60%, based on equation (1).
Claims (11)
1. A process for making alkyl phosphines of the general formula Rn PH3-n (I), in which R is identical or different alkyl groups having 1 to 3 carbon atoms, especially 1 carbon atom, and n is a whole number of 1 to 3, which comprises: reacting phosphorus in vapor form with steam and an alkyl amine of the general formula Rn NH3-n (II), in which R and n have the meanings given above, at elevated temperature in contact with a carbon catalyst placed in a reactor, the reactants being used individually or in admixture with one another.
2. The process as claimed in claim 1, wherein the reaction is effected at temperatures of 280° to 350° C.
3. The process as claimed in claim 1, wherein phosphorus, steam and alkyl amine are used in quantities corresponding to a molar ratio of P4 :H2 O:alkyl amine of 1:1:1 to 1:30:30.
4. The process as claimed in claim 1, wherein the reactants are passed through the reactor at a velocity necessary to ensure a contact time with the catalyst of 1 to 200 seconds.
5. The process claimed in claim 4, wherein the reactants are passed through the reactor at a velocity necessary to ensure a contact time with the catalyst of 5 to 100 seconds.
6. The process as claimed in claim 1, wherein the reactants are mixed in gas phase, the resulting mixture is heated to reaction temperature and then contacted with the catalyst.
7. The process as claimed in claim 1, wherein active carbon is used as the catalyst.
8. The process as claimed in claim 7, wherein the active carbon has a BET-surface area of more than 10 m2 /g.
9. The process as claimed in claim 1, wherein the phosphorus is reacted with a slight stoichiometric excess of alkyl amine and contacted with the catalyst over a period of about 5 to 50 seconds, with the resultant formation predominantly of primary phosphines.
10. The process as claimed in claim 1, wherein the phosphorus is reacted with a large stoichiometric excess of alkyl amine and contacted with the catalyst over a period of more than 50 up to about 100 seconds, with the resultant formation predominantly of tertiary phosphines.
11. The process as claimed in claim 1, wherein a primary, secondary or tertiary methyl amine is used as the alkyl amine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772721425 DE2721425A1 (en) | 1977-05-12 | 1977-05-12 | PROCESS FOR PRODUCING ALKYLPHOSPHINES |
| DE2721425 | 1977-05-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4150058A true US4150058A (en) | 1979-04-17 |
Family
ID=6008755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/904,027 Expired - Lifetime US4150058A (en) | 1977-05-12 | 1978-05-08 | Production of alkyl phosphines |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4150058A (en) |
| BE (1) | BE866923A (en) |
| CA (1) | CA1071655A (en) |
| DE (1) | DE2721425A1 (en) |
| FR (1) | FR2390451A1 (en) |
| GB (1) | GB1572325A (en) |
| IT (1) | IT7849280A0 (en) |
| NL (1) | NL7805029A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012118671A1 (en) | 2011-02-28 | 2012-09-07 | Coopervision International Holding Company, Lp | Phosphine-containing hydrogel contact lenses |
| WO2013114311A1 (en) * | 2012-02-02 | 2013-08-08 | Ecole Polytechnique | Method for preparing tertiary phosphines and derivatives of same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2731458A (en) * | 1952-12-30 | 1956-01-17 | Socony Mobil Oil Co Inc | Alkylation of yellow phosphorus with olefins |
| US3079311A (en) * | 1961-02-20 | 1963-02-26 | Nalco Chemical Co | Method of preparing tertiary phosphines |
| US3099690A (en) * | 1962-07-24 | 1963-07-30 | American Cyanamid Co | Preparation of organic phosphorus compounds from phosphorus, an alkyl halide, and anorgano-magnesium halide |
| US3760001A (en) * | 1971-04-03 | 1973-09-18 | Knapsack Ag | Production of trialkylphosphines |
| US3855311A (en) * | 1972-11-11 | 1974-12-17 | Hoechst Ag | Production of dialkylphosphines |
| US4052463A (en) * | 1975-10-06 | 1977-10-04 | Stauffer Chemical Company | Process for preparing tertiary phosphine sulfides and oxides |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2116355C3 (en) * | 1971-04-03 | 1979-05-31 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of trialkylphosphonium halides |
-
1977
- 1977-05-12 DE DE19772721425 patent/DE2721425A1/en not_active Withdrawn
-
1978
- 1978-04-27 GB GB16740/78A patent/GB1572325A/en not_active Expired
- 1978-05-05 CA CA302,736A patent/CA1071655A/en not_active Expired
- 1978-05-08 US US05/904,027 patent/US4150058A/en not_active Expired - Lifetime
- 1978-05-10 NL NL7805029A patent/NL7805029A/en not_active Application Discontinuation
- 1978-05-10 BE BE187572A patent/BE866923A/en unknown
- 1978-05-10 IT IT7849280A patent/IT7849280A0/en unknown
- 1978-05-12 FR FR7814323A patent/FR2390451A1/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2731458A (en) * | 1952-12-30 | 1956-01-17 | Socony Mobil Oil Co Inc | Alkylation of yellow phosphorus with olefins |
| US3079311A (en) * | 1961-02-20 | 1963-02-26 | Nalco Chemical Co | Method of preparing tertiary phosphines |
| US3099690A (en) * | 1962-07-24 | 1963-07-30 | American Cyanamid Co | Preparation of organic phosphorus compounds from phosphorus, an alkyl halide, and anorgano-magnesium halide |
| US3760001A (en) * | 1971-04-03 | 1973-09-18 | Knapsack Ag | Production of trialkylphosphines |
| US3855311A (en) * | 1972-11-11 | 1974-12-17 | Hoechst Ag | Production of dialkylphosphines |
| US4052463A (en) * | 1975-10-06 | 1977-10-04 | Stauffer Chemical Company | Process for preparing tertiary phosphine sulfides and oxides |
Non-Patent Citations (1)
| Title |
|---|
| Chemical Abstracts, 67, 108715j (1967). * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012118671A1 (en) | 2011-02-28 | 2012-09-07 | Coopervision International Holding Company, Lp | Phosphine-containing hydrogel contact lenses |
| US8642677B2 (en) | 2011-02-28 | 2014-02-04 | Coopervision International Holding Company, Lp | Phosphine-containing hydrogel contact lenses |
| US9864103B2 (en) | 2011-02-28 | 2018-01-09 | Coopervision International Holding Company, Lp | Phosphine-containing hydrogel contact lenses |
| WO2013114311A1 (en) * | 2012-02-02 | 2013-08-08 | Ecole Polytechnique | Method for preparing tertiary phosphines and derivatives of same |
| FR2986527A1 (en) * | 2012-02-02 | 2013-08-09 | Ecole Polytechnique Dgar | PROCESS FOR THE PREPARATION OF TERTIARY PHOSPHINES AND DERIVATIVES THEREOF |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7805029A (en) | 1978-11-14 |
| BE866923A (en) | 1978-11-10 |
| CA1071655A (en) | 1980-02-12 |
| FR2390451A1 (en) | 1978-12-08 |
| GB1572325A (en) | 1980-07-30 |
| IT7849280A0 (en) | 1978-05-10 |
| DE2721425A1 (en) | 1978-11-16 |
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